Monoazo compounds



Patented Aug. 20, 1946 MONOAZO COMPOUNDS Joseph B. Dickey and James G. McNally,'Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application May 20, 1942, Serial No. 443,718

.6 Claims. (01. 260205) This invention relates to new azo dye compounds and their application to the art of dyeing. We have discovered that dyeings which can be discharged to a clear white can be obtained by dyeing a suitable textile material with a dye having the formula:

alkyl RN=NR1N v R: v wherein R stands forv the residue of a benzene nucleus containing an NHz group inpara position; to the azo bond shown and a .from the group consisting of hydrogen and an .alkyl group and R4 stands for a member selected from the groupconsisting of an alkyl group .and a benzene nucleus, in 'ortho or meta position to the azo bond shown, R1 stands for the residue of a benzene nucleus and R2 stands for a member selected from the group consisting of an alkyl group and a benzene nucleus, diazotizing the dye on the fiber and developing with a developer component. r I

So far as we are aware both the monoazo dye compounds and the disazo dye compounds resulting from the development operation constitutenew compounds. Accordingly, it isan object of our invention to provide new azo dye compounds. Another object is to provide dyeings on textile materials which are of good fastness to light and washing and which can be discharged to a clear white. A particular object is to provide cellulose acetate textile materials dyed navy blue or blackshades of good fastness to light and washing and which are dischargeable to'a, clear white.

The dyeing process of our invention appears to, be particularly of value in connection with textile materials.

Typica1 organic derivatives of cellulose include thehydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acewhite is a very them are highly desirable.

- 2 tate, cellulose formate, cellulose propionate or cellulose butyrate and the hydrolyzed as well: as the unhydrolyzed mixed organic acidesters of cellulose such as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such'as methyl cellulose, ethyl cellulose or benzyl cellulose. While our invention will be described more particularly ingconnection: with the dyeing of cellulose acetate, silk, it willbe understood that it is applicable to the Idyeing of the other textile materials'which have been indicated hereinbefore.

Dependingupon' the particular developer component used to develop the diazotized dye' on the fiber yellow, scarlet, violet, navy blue and black dyeings can be obtained. The use of components, such as '2-hydroxy-3-carboxynaphthalene, yielding dischargeable navy' blue to black shadesappears to be of greatest importance-since these shades are in demand and dyes which can. yield The disazov dyes resulting from the development operation have the formula:

T alkyl I D-N=NV BN=N R1N/ R2 wherein D stands for the residue of a developer component, B stands for the residue of a benzene nucleus containing a, I

-SO2N/ R4 group and wherein R1, R2, Rsand R4 have the meaning previously assigned to them.

The dye compounds of our invention possess properties which make them of unusual industrial importance. The free amino dye. compounds combine ,good speed of dyeing with good exhaustion and for the most part can be applied to the fiber at. a temperature as low as C.

Further, generally speaking, these free amino dye compounds possess good solubility in water .anddo not gum'on heating with steam; When diazotized on the fiber and coupled with a developer component, such as 2-hydroxy-3-carboxynaphthalen'e, desirable shades of color are obtainedwhichare of good fastnessto light and washing and which arereadily dischargeable to a clear white. Ready dischargeability to a clear important property for a dye to possess. V y

The qualities above enumerated,- as previously noted, makethe-dye compounds of'ourinvention very valuable commercially; Rapid dyeing which takesiplace is very vigorous.

Accordingly, the discovery of dye compounds which .dye. rapidly at low temperatures, which exhaust well,

which have excellent solubilityin water; which do not form gummy deposits. andlwhichxyield.

dyeings of excellent fastness to light and'w'ashing and which are readily dischargeable to white constitutes an important as well as unexpected technological advance.

Concentrations, for example, from to 3% by weight of the dye tothe material undergoing dyeing can be employed-in the initial dyeing operatic-n, prettyuorangewellow dyeings being obtained. For the development operation following thediazotization of the free amino dye compounduon Jthe fibenan excess of the developer component is ordinarily employed. The intensity of shade-obtained varies depending on theiamountof the free amino dye-absorbed by :the fiber: in the initial 'd yeingoperation. To illustrate, when 2 hydroxy 3 -carboxynaphthallenetis the developer component 'at lower concentrations, the color "appears navy blue but as the concentration increases the intensity of the color increases until :thecolor appears black. Thus'it is seen that the'intensity of the sgiade increases" with anincrease in the amount :of the free-amino dyeiappliedto the fiber. 7 Themonoazo"dye compounds of our invention can be prepared by reducing the corresponding nitro dye compounds to the free amino form. Thus 4 amino-2 -sulfonemethylainidobenzene- -azo-4-zdimethylaminobenzene having the ior- 'mul'az Id H.N r nk 3: 34

I I /H CH: SOgN 'CHt f can be prepared by reducing I v 7 CH:

. Example 1 17.? grams of '4 -nitro-2' sulfonemethylamidobenzeneazol dimethylaminobenzene are heated in 100 ccrof ethyl alcoholto boiling. A solution of 8 gram-s'of 60% sodium sulfide fusedwith 2 :gramsof sulfurin 20 cc. of'water is then added in small portions because the reduction reaction "minutes afterwhich it is'p'oured through a filter paperinto two liters of coldwater'which is stirred lvigorously. Vigorous s'tirring i required because After all of 4 the dye compound formed tends to coagulate as a gummy mass unless it is well stirred to keep the product broken up. 11.3 grams, which is 67.45% of the theoretical yield of 4'-amino-2'-sulfonemethylamidobenzeneazo 4 dimethylaminoben- .zeneis obtained in the form ofsmallfinely formed red-orange crystals. The dye compound formed is recovered by filtration, washed with water and dried.

By substituting an equivalent gram molecular weight of 4-nitro-2-sulfonemethylamidobenzeneazoe i-diethylaminobenzene for the starting dye'compound' of the example 4'-amino-2'-sulfonemethylamidobenzeneaz 4 diethylaminobenzene is obtained. This dye compound is likewise obtained as red-orange crystals and has properties substantially the same as the dye compound benzeneazo-4-diethylaminobenzene.

of the example.

I V ExampZeZ 23 grams of i-nitro-'2-sulfonethylamidobenzeneazo '-4-di-chydroxyethylaminobenzene are heated in 100 cc. of ethyl alcohol in a reaction vessel to boiling. A solution 0 58 grams offused 60% sodium sulfide in 18 cc, of water is'then added in small portions because the reduction reaction proceeds very vigorously. After all of the sulfide solution has been added, the reaction mixture is boiled for 45-60 minutes and then poured through a filter paper into two liters of cold water which is vigorously stirred. 13 grams, which is 65% of the theoretical amount of 4-'amino-2"- sulfonethylamidobenzeneazo-4-di ,8 hydroxyethylaminobenzene is recovered by filtration as well formed orange crystals. The dye compound obtained is washed with'water and dried.

Example 3 getherwith 200cc; of ethylalcohol and the mixture resulting'is heated to boiling. 8 grams of fused 60% sodium sulfide in 18cc. of water is then added in small portions to prevent the reduction-reaction from being too vigorous. vAfter all of the sulfide -'solution has been added the reaction mixture is refluxed for 45-60 minutes and then'poured through a'filter paper into 2 liters of cold water which is being stirred'vigorously. 17.5 grams, which is 82% of the theoretical amount of '4'-a-mino 2' sulfonethylamidobenzeneazo' 2- chloro-'4-(ethyl, p-hydroxyethyl) aminobenzene is obtained after filtration of the'reaction mixture in the form of wel1iormed red-orange crystals.

The dye --compound obtained is washed with water and dried.

Following the procedure described in Examples 1, 2 and 3; the following monoazo dyes of our inbenzeneazo l-dimethylaminobenzene.

2. 4' amino-2'-sulfone-p-methoxyethylamidobenzeneazo-4-dimethylaminobenzene.

3. 4 amino-2-sulfone-;8-methoxyethylamido- 4.- 4"- amino-2"-sulfone-p-methoxyethylamidobenzeneazo-i- (ethyl, fi-hydroxyethyl) -aminoben zene. V

'5. 4 amino-2'-sulfone;3methoxyethylamidobenzeneazo-4-di-p-hydroxyethylaminobenzene.

-- ."Whilfi a'considerable number of compounds ilillustrating the monoazo dyecompounds of our invention have been given, it is to be clearly understood that the compounds disclosed ar illustrativeand not limitative of the invention. Thus, .any of the nitrobenzene-sulfoneamide compounds disclosed herein'can be diazotized and coupled with any of the coupling components indicated herein to yield 'monoazo dyes which can be converted in accordance with the Procedure described inExamples 1, 2 and 3 to yield the monoazo dye compounds of our invention.

:The monoazo dye compounds of the invention can bezapplied to the textile material such as an organic derivative of cellulose textile material by methods well known in the art. They may be appli d, for example, from an aqueous solution orsuspension of the dye or dyes. In this method the dye i finely ground and ordinarily intimately admixed'with a dispersing or solubilizing agent such as soap, sodium sulforicinoleic acid or sodium lignin-sulfonate and dispersed in water to form an aqueous dyebath. The material-to be dyed is then added to the dyebath thus prepared and dyeing is conducted at a temperature of 50:85". C. until complete. In accordance with the usual dyeing practice, the material to be dyed will ordinarily be added to the dyebath at a temperature lower than that at which the main portion of the dyeing is to be effected, a, temperature approximating 45-55" C., for example, following which thetemperature of the dyebath is raised to "that selectedfor carrying out the dyeing operation. Usually one to two hours is sufiicient for the dyeing operation. As this method of dyeing and modifications of it arewell known to those skilled'in the artto which this invention is directed, further discussion is believed unnecessary.

The monoazo dye compounds Of the invention are principallyof importance in connection with so-called developed dyeing operations. In this method of dyeing the monoazo dye (or dyes) is diazotizedom the fiber and the diazonium compound resulting is coupled with a compound known as a developer compound. These latter compounds are well known to those skilled in the .art asa considerablenumber of them are disclosed in the prior art. Representative developer compounds arejgiven hereinafter but no attempt .has been made to givean exhaustive list. It will be apparent that compounds of the general char- .acter. as those indicated can also be employed.

. ,Developer compoundsthat canbe employed include 2-hydroxy 3 carboxynaphthalene, 1- phenyl-S-methyl-5-pyrazolone, phenol, a cresol such as p-cresol, 3-naphthol, arylamides of 2-hy- ,droxy-3-carboxynaphthalene such as the anilide, the m-nitroanilide or the p-methoxyanilide derivatives, 1 di ehydroxyethylamino 2- methoxy-fi-methylbenzene, N-di-B-hydroxyethylaminobenzene, N-(ethyL e-hydroxyethyl) -aminobenzene, N- 3, -dihydroxypropyltetrahydroquinoline, 1-b,' dihydrogpropyl-2-methyltetrahydro- ,quinolineand 1-B-hydroxyethyl-2fl dimethyltetrahydroquinoline.

I The colors obtainable when representative monoazo dyes of our invention are applied to cel lulose acetate textile materials, diazotized on the fiber and then developed with various representative developer compounds are givenhereinafter.

are given in the paragraph immediately followv ing.

"1. .4 efamino' :12 J-- sulfonemethylamidoben zeneazoeledimethylaminobenzene.

2. 4 amino 2' sulfonethylamidobenzene azo-4-di-p-hydroxyethylaminobenzene.

3. 4' amino 2 sulfonethylamidobenzene azo 2 chloroi- (ethyLe-hydroxyethyl) -aminobenzene. a

4.4 amino .2 sulfonemethylamidoben zeneazo-4-diethylaminobenzene.

5. 4 amino 2 ,sulfonephenylami'dobenzeneazo 4 (ethyLe hydroxyethyl) aminobenzene.

' 6. 4' amino ,3' sulfonethylamidobenzene azo-4-dimethylaminobenzene,

7. 4'.- amino 3' sulfonethylamidobenzene azo-4-di-p-hydroxyethylaminobenzene.

8. 4 amino 3' -sulfonethy1amidobenzene azoei-(methylphenyl) -aminobenzene.

9. 4' amino 3' sulfonethylamidobenzene azo-l-di-B-hydroxyethylaminonaphthalene.

10. 4' amino 2' sulfonethylamidobenzeneazo-4-di-p-hydroxyethylaminonaphthalene.

ll. 4 amino 6 chloro 2 sulfonemeth y1amidobenzeneazo-4-dimethylaminobenzene.

12. 4 amino 2 sulfonedimethylamidobenzeneazol-di-fi-methoxyethylaminobenzene.

When the above compounds are diazotized and coupled with 2-hydroxy-3-carboxynaphthalene, navy blue to black dyeings are obtained; when coupled with I-phenyI-B-methyl-S-pyrazolone, yellow dyeings are obtained; when coupled with e-naphthol, scarlet dyeings are obtained; when coupled with 1-di pehydroxyethylamino-2methoxy-S-methylbenzene, violet dyeings are obtained and when 1 firv-dihydroxypropyl-Z-methyltetrahydroquinoline is the developer component navy blue dyeings are obtained. 1

The monoazo dye on the fiber can be diazotized in accordance with the procedure described hereinafter. Itwill be understood, however, that any other suitable method can be used.

Diazotization of the monoazo dye on the fiber After the material has been rinsedafter dyeing, it is diazotized in a hath made up as follows: For each 10 grams of cloth, one gram of sodium nitrite is dissolved inra mixture containing 2 grams of concentrated (35 hydrochloric acid and 300 (Bo/ of water. The diazotization treatment is given for 30-45-minutes at a temperature of about'20 C. Upon completion of the diazotization reaction, the fabric is removed and thoroughly rinsed'with water following which it is ready for development.

The development operation of the invention will be illustrated in connection with 2 hydroxy- 3-carboxynaphthalene. Generally speaking, the developing operation will be carried out in a moderately acid medium although in certain cases it may be deemed more desirable to carry out the development operation in a slightly alkaline medium. a

Following thediazotization treatment, the material is developed, preferably immediatelyfln a bath made up as follows: for every 10 grams of cloth, 10 cc. of a 5% stock solution of Z-hydr'oxy- S-naphthoic acid and 1 cc. of glacial acetic acid are added to 300 cc. of Water. The stock solution of 2-hydroxy-3enaphthoic acid is made by dissolving 10 grams of 2-hydroxy-3-naphthoic acid inlOO .cc. of 5% .NaOH and then adding cc. of water. The cellulose acetate cloth from the diazotization treatment is entered in the developing bath.at -30jC; and "the temperature is gradually raised to 60 (Lover a 30 minutepe riod at which temperature the bath is kept for another 30 minutes. Following this treatment, the cellulose acetate silk is removed, washed well with water and dried.

The developing bath made up as described above has a pH of approximately 4.0. By increasing the amount of acetic acid, the pH will be lowered and the shade obtained on the fabric will be greener. If the pH is raised by decreasing the amount of acid added a redder shade is obtained. Using the above procedure, navy blue to black shades can be obtained depending upon the concentration of the monoazo dye on the fiber. The colors obtained are readily discharged to substantially a pure white by the usual reduction discharges such as, for example, the monozinc salt of the formaldehyde sulfoxylic acid (Rongalite).

While the development operation has been 11- lustrated in connection with the use of 2-hydroxy-3-carboxynaphthalene, it will be understood that it can be carried out in a similar manner using one of the other developer components indicated herein. That is, the pH of the developer bath can be about 4.0 although as previously indicated the pH is not restricted to this value. The shade obtained will vary somewhat depending upon the pH of the developer bath. If desired, the dyeing can be topped by treating with a direct dye of another shade. Also the development operation can be effected using more than one developer compound. To illustrate, the diazotized fiber can be developed with both 2-hydroxy-3-carboxynaphthalene and 1-phenyl-3- methyl--pyrazolone at the same time.

Although the use of the dye compounds of our invention has been described more particularly in connection with cellulose acetate, it will be understood that they can be applied to the other textile materials named herein by the methods described or by methods similar thereto. Further, while the disazo dye compounds of our invention have been shown as being prepared on the fiber, it will be understood that the diazotized monoazo dyes can be coupled with the developer components without being applied to the fiber and if this is done the disazo dyes are obtained per se. Normally the disazo dye is formed on the fiber.

Coupling components wherein the benzene or naphthalene nucleus contains an amino group which is substituted with a phosphorus grouping can be prepared as described in our copending application Serial No. 225,198, filed August 16, 1938.

We claim:

1. The azo compounds having the formula:

| I I R5 l 1 SOaN 10 selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxyalkyl group and a lower hydroxyalkyl group, R4 and R5 each stands for a member selected from the group consisting of a lower alkyl group, a lower alkoxyalkyl group, a lower hydroxyalkyl group and a monocyclic group of the benzene series, X1 stands for a member selected from the group consisting of hydrogen, a lower alkyl group, an acetamino group and a chlorine atom, X2 stands for a member selected from the group consisting of hydrogen and a lower alkoxyl group, 2Q stands for a member selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxyl group, a chlorine atom and a bromine atom, and X4 stands for a member selected from the group consisting of hydrogen and a lower alkyl group and wherein at least one of X3 and X4 must be hydrogen.

2. The azo compounds having the formula:

wherein R2 and R5 each represents a lower hydroxyalkyl group and R3 represents a lower alkyl group.

4. The azo compound having the formula:

CH: 0 H2 0 H N=N N\ C2115 S OzN HgN CH CHzOH 5. The azo dye compound having the formula:

6. The azo dye compound having the formula:

CgHs H.N@ N=N@ N O f) H CgH5 JOSEPH B. DICKEY. JAMES G. MCNALLY. 

